CN1503693A - Process for making and using a low beverage soluble iron content adsorbent and composition made thereby - Google Patents
Process for making and using a low beverage soluble iron content adsorbent and composition made thereby Download PDFInfo
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- CN1503693A CN1503693A CNA02803659XA CN02803659A CN1503693A CN 1503693 A CN1503693 A CN 1503693A CN A02803659X A CNA02803659X A CN A02803659XA CN 02803659 A CN02803659 A CN 02803659A CN 1503693 A CN1503693 A CN 1503693A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12H—PASTEURISATION, STERILISATION, PRESERVATION, PURIFICATION, CLARIFICATION OR AGEING OF ALCOHOLIC BEVERAGES; METHODS FOR ALTERING THE ALCOHOL CONTENT OF FERMENTED SOLUTIONS OR ALCOHOLIC BEVERAGES
- C12H1/00—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages
- C12H1/02—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material
- C12H1/04—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material
- C12H1/0408—Pasteurisation, sterilisation, preservation, purification, clarification, or ageing of alcoholic beverages combined with removal of precipitate or added materials, e.g. adsorption material with the aid of ion-exchange material or inert clarification material, e.g. adsorption material with the aid of inorganic added material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
Abstract
An adsorbent removes certain undesirable components from beverages, such as beer, and has a low beverage soluble iron (BSI) content. These undesirable components include contaminants which cause chill haze. The adsorbent includes two components, a silica component and a polyphosphate sequestering agent component, such as sodium tripolyphosphate (STPP). The process for using the adsorbent involves first contacting a beverage with an adsorbent to adsorb at least a portion of the undesirable components then separating the adsorbent from the beverage. The adsorbent may be formed by one of two methods or a combination of both. The first method involves adding the polyphosphate sequestering agent to a reactant, such as a sodium or potassium silicate solution, prior to or during the gelation stage. A second method involves adding the polyphosphate sequestering agent to the water wash after a hydrogel is formed. The BSI of the adsorbent is substantially reduced using the first method, but the total iron content of the adsorbent appears to increase. The second method decreases both the BSI and the total iron content of the silica gel.
Description
Technical field
The present invention relates in alcoholic beverage such as beer, have the adsorbent of LA soluble iron content.
Background technology
Silica gel has been used for removing some undesirable component by some alcoholic beverage, typically by absorption.For example, silica gel has been used for brewing method, comes stable beer to form muddy low molecular weight protein (for example being lower than 40,000 dalton) usually by absorption.Commercially available silica gel is by silicate solutions and inorganic acid manufacturing, and contains a spot of metal such as iron, and described metal partly dissolves in the alcoholic beverage and pollutes them.The iron content of the silica gel of solubility partly is commonly referred to " alcoholic beverage soluble iron " (abbreviating " BSI " usually as) in the alcoholic beverage.Though the BSI of adsorbent can easily discern, BSI with the different alcoholic beverage in other factors, pH, and temperature change.So the metal of dissolving can make the gel component instability of alcoholic beverage, comprises that can to make quality lower.For example, the iron of high dissolution degree influences beer taste and pot-life unfriendly.
Having done some effort with stable beer, more specifically is to handle beer to prevent chill haze and metallic pollution.For example, the United States Patent (USP) of Bradley discloses for the 4th, 134, No. 857 by the aqueous solution with tannic acid or gallic acid or their mixture, and washs filter aid such as diatomite reduces BSI by means of the citric acid of control color.
The existence of high content iron can be harmful to the taste and the long-time stability (" pot-life ") of alcoholic beverage in the alcoholic beverage.Therefore, it is favourable making cost-effective adsorbent have low BSI.
Summary of the invention
Consider goal of the invention, the invention provides adsorbent, be used for removing some component to lower chill haze by alcoholic beverage with LA soluble iron (BSI) content.This adsorbent is made by introduce the polyphosphate chelating agent during making adsorbent.Particularly, the wash solution that this method comprises the reactant that makes polyphosphate chelating agent such as sodium phosphate trimer and silica gel or contains the silica gel parent contacts, or contacts with the two.Reactant can be sodium metasilicate or potassium silicate solution, is used for preparing silica hydrogel with inorganic acid.Parent can be by sodium metasilicate or potassium silicate solution and mixes the silica hydrogel that forms with inorganic acid.Form adsorbent by this parent.Therefore, composition of the present invention is the adsorbent that comprises silica component and polyphosphate chelator component.
The present invention also provides and uses this adsorbent to reduce some impurity in the alcoholic beverage.Method and composition of the present invention is used for removing the impurity that trends towards forming at beer chill haze.Described method comprises contacts to be adsorbed to the small part component alcoholic beverage with adsorbent of the present invention, then by separating adsorbent in the alcoholic beverage, for example by filtering.
Should understand aforesaid general remark and following detailed description all is exemplary illustration the present invention, rather than restriction the present invention.
Description of drawings
In conjunction with the accompanying drawings, can best understanding be arranged to the present invention by the following specific embodiment, wherein:
Fig. 1 is the schematic diagram of first embodiment of the method for preparing adsorbent of the present invention; And
Fig. 2 is the schematic diagram of second embodiment of the method for preparing adsorbent of the present invention.
The specific embodiment
The present invention relates to be used for removing the impurity of alcoholic beverage and prevent to form chill haze, iron is minimized by the leaching of adsorbent to alcoholic beverage.Attempt to contain the alcoholic beverage that all comprise some protein at this used term " alcoholic beverage ", if protein is present in the alcoholic beverage, then its trend is muddy owing to refrigeration forms, but protein can be adsorbed by the present invention.This type of alcoholic beverage comprises many based on vegetables or based on the alcoholic beverage of Fructus Hordei Germinatus, as beer, ale, and grape wine and fruit juice.The present invention is specially adapted to beer, comprises Lager, Pilsner beer, M and ale, porter and strong kornbranntwein.
" removing " in this used term " is removed component " in by alcoholic beverage means the optional ingredient of removing at least some percentage compositions, as causes the protein of chill haze, but needn't expect absolutely to remove any of these component.Yet,, can remove the degree that a certain component to any known quantitative analysis procedure all can't detect in some cases.
As described below, when preparation silica gel absorber of the present invention, the present invention uses the polyphosphate chelating agent.The polyphosphate chelating agent is to comprise anion P
nO
3n+1Compound, and can the chelating cation, foremost in this example is iron cation or ferrous cation.The polyphosphate chelating agent can comprise alkali metal or alkaline-earth metal in its prescription.Have been found that sodium phosphate trimer Na
5P
3O
10Be suitable for purpose of the present invention.
Below in conjunction with Fig. 1 and 2 method for preparing adsorbent of the present invention is discussed.Usually, these methods comprise that the wash solution (or the two mixture) that at first makes polyphosphate chelating agent and silica gel reactant or contain the silica gel parent contacts, and forms silica gel absorber by parent then.The silica gel reactant can comprise the parent material that can react with other parent materials of formation silica gel parent.Reactant comprises sodium metasilicate or potassium silicate solution, and when combining or forcing by nozzle with acid under certain condition, it forms hydrogel.Parent is for having the material of identical chemical composition basically with final silica gel, but but some physical change, as the variation of porosity measurement performance (porosimetry property), the variation of water capacity or the physics retentivity of other compounds in its hole.Formation realizes by conventional method, and comprise following discussion hydrothermal treatment consists (though in embodiment discussed below, not implementing), washing, grindings, reach drying.
In the embodiment depicted in fig. 1, polyphosphate chelating agent such as sodium phosphate trimer (STPP) mix the formation mixture with sodium metasilicate or potassium silicate.Chelating agent source 104 can provide STPP solution soluble in water.This solution in conjunction with the sodium metasilicate or the potassium silicate that are provided by silicate source 102, forms the silicate mixture that STPP-mixes in blender 106.Silicate mixture the mixings time enough that this STPP-is mixed to be obtaining the mixing of abundance, and for example 2-6 hour, although this visual other factors and changing.The amount of polyphosphate chelating agent to be added depends on the iron content of silicate, and it can be measured by conventional quantitative analysis tech.The amount of sodium phosphate trimer that can join sodium metasilicate or potassium silicate solution is for to make sodium phosphate trimer: the mol ratio of iron is about 0.5: 1-50: between 1, and preferred about 5: 1-10: 1.
Next, by forming silica gel as the silicate mixture that mixes with STPP-in the inorganic acid with acid.In following examples, use sulfuric acid.Except adding in silicate solutions the STPP, the manufacturing that contains the silica gel absorber of STPP component can anyly be used to prepare the known way influence of conventional silica gel absorber.For example, acid source 100 can be used for providing acid, and this acid can combine with the silicate mixture that STPP-mixes and form the hydrosol.Especially, the aqueous solution by rapid mixed acid and sodium metasilicate or potassium silicate forms silica hydrosol.Found that the concentration of conditioned reaction thing in this invention and flow velocity or ratio make the hydrosol contain to have an appointment the SiO of 5-30 weight %
2, the preferred SiO of about 10-20 weight %
2Be favourable.Find that also preferred neutralization fully is present in all alkali metal in the silicate solutions, and the excess acid that preferably is higher than 5 moles of %-30 moles of stoichiometry required amount % (preferred 15-25 mole %) come fully in and sodium or potassium.Therefore, preferably in silica hydrosol, there is not or do not have substantially unreacted Na
2O or K
2O.
As shown in Figure 1, has the hydrosol pressurized of polyphosphate component by nozzle 108.Nozzle thus, the hydrosol drop on the moving belt 109 and allow to place in a known way and form hydrogel.Be further processing, this hydrogel allows that the aging sufficiently long time is to become hard on conveyer belt.Among an embodiment, the hydrosol contains 18% the SiO2 of having an appointment, and it is about 1 that its pH value is lower than, and become gel in a few minutes.This type of hydrosol forms globule on conveyer belt 109.
Hydrogel washs with acidifying water in washer 112 then, desalts by removing in this hydrogel.Can implement repeatedly to wash as prior art, salinity be an acceptable level or following in flowing out liquid, is preferably zero or approaching zero.Can batch process, flow synchronously or reverse flow is implemented washing.Found that acidifying water wishes, for example used sulfuric acid.The pH value of washings can be 2.5-4.0, preferred 3.2-3.4.
Hydrogel through washing flows into lapping device 116 via pipeline 114 then, in this grinding.Although granularity will depend on the needs of final use and other conditions of alcoholic beverage purge process, grinding and can continue until particle mean size is about 40 microns of about 10-.Usually, particle should be powdery, and should not grind to such an extent that too little feasible filtration becomes difficulty.Adsorbent is packing in packing device 120 then.The BSI that has attenuating according to the formed adsorbent of embodiment shown in Figure 1.
In embodiment shown in Figure 2, the polyphosphate chelating agent mixes with the acidifying washing lotion that contrasts as silicate solutions, and other processing conditions are normally identical.Particularly, reactant is as mixing with acid from acid source from the sodium metasilicate of silicate source 200 or potassium silicate.Make this mixture pass through nozzle 203 to form the hydrosol, it is all placed in a known way and forms hydrogel, typically on driving-belt or container 205.As mentioned above that this hydrogel is aging then, and guiding washer 208.Except the flow velocity of conditioned reaction thing makes the SiO2 that has 15-20% in the hydrosol, all related concentrations all with embodiment shown in Figure 1 in identical.
Washer 208 does not contain the acidifying washings, and contains water and acidifying mixture from device 206 polyphosphate chelating agent.The polyphosphate compound can be STPP.Sodium phosphate trimer can be with in this acidifying mixture of a certain amount of adding, to reach the concentration to acceptable level measured that enough lowers BSI.Except other factors, the specific concentrations of polyphosphate chelating agent will depend on the amount that (comprises on the silica gel and reaching in the acidifying water) iron in the washings 208.In embodiments of the invention, be benchmark with the sodium metasilicate, the concentration of sodium phosphate trimer is 0.01-1 weight %, preferred 0.05-0.5 weight %.In another embodiment and be used for following examples, can obtain the amount of STPP to be added by the molal quantity of measuring iron in the initial water gel.In the case, the molal quantity (being the total amount of used STPP during the washing step) of regulating STPP is 5 than the molal quantity of iron: 1-20: 1.Thereby used washings are many more, and the concentration of STPP is low more.
Acidifying mixture can be by at first being dissolved in the water STPP, the STPP concentration of any place is between 10-800ppm, preferably between about 100-400ppm (though this concentration can change based on the iron in silicate or the hydrogel as mentioned above), then with the pH value of sulfuric acid regulation solution between the 2.5-4.0, preferred 3.3-3.5.By forming silica gel with chelating agent mixture washings gel 204.
As previously mentioned, the hydrogel through washing enters lapping device 210 then and finally enters packing device 214.Embodiment shown in Figure 2 shows have been reached about reducing all iron contents and the alcoholic beverage soluble iron content of adsorbent.Also can make adsorbent in conjunction with Figure 1 and Figure 2 embodiment feature.In other words, the silicate solutions that mixes of STPP-can be used for forming the hydrogel of the water washing that available STPP mixes.
Be sure of that the wide silica gel of porosity determination performance range can be used for the present invention.More specifically, be sure of for the object of the invention, be not strictly limited to pore volume, aperture, surface area or the granularity of particular range.Yet, found that pore volume is that about 1.5-2.5cc/g, average pore size are 750-850m for about 75-125 dust, surface area
2/ g and water capacity are about 60-70%] H
2The silica gel of O is fit to.The water washing that the present invention also can be used for mixing with STPP is after hydrothermal treatment consists (as described below) reduces the xerogel of surface area.The pore volume of this xerogel can be about 1.0-1.4cc/g, and average pore size is about 75-125 dust, and surface area is about 250-450m
2/ g.
Obtaining this type of silica gel is known in this area.For example, under the alkaline pH value silica gel is being exposed under the high temperature, is causing the average pore size of rearrangement, surface area attenuating and the end product of gel structure to increase.The method is called " hydrothermal treatment consists " in this area.For this reason, acid deposition silica gel need be adjusted to alkalescence or pH neutral.Drying condition also will influence the porosity determination performance; Drying trends towards obtaining higher pore volume rapidly.The dioxide-containing silica of the hydrosol also influences porosity determination.All these influences all are well known by persons skilled in the art and description are all arranged in many publications and patent.
In by alcoholic beverage, remove and use adsorbent in the method for component, have relative low BSI simultaneously to lower chill haze." low BSI " is for the BSI that uses the adsorbent that makes except method identical not being exposed to the polyphosphate chelating agent at term used in the context.Particularly shown in following examples, adsorbent of the present invention can have the BSI than the BSI low 50% of comparable adsorbent, preferably is lower than 25%, more preferably less than 10%.With conventional method, the preferred method that promotes absorption contacts the method that realizes removing impurity by making adsorbent of the present invention simply with alcoholic beverage.Adsorption step can be any method in batches or continuously easily.Under any circumstance, stirring or other mixing all will strengthen the adsorption efficiency of adsorbent.
Absorption can be implemented under alcoholic beverage is any preference temperature of liquid.Typically, the alcoholic beverage temperature is about 29-40 °F.Alcoholic beverage contacts a period of time as mentioned above with adsorbent, and this time is enough reached the attenuating of desired percentage composition in the alcoholic beverage of handling.The change of concrete time of contact depends on that sometimes institute's choosing method is each component concentrations in the type of batch process or continuity method, pending alcoholic beverage and condition, the alcoholic beverage, used particular adsorbent.If be provided with when time of contact, the granularity of adsorbent can change in a known way to meet various processing conditions.In addition, the relative quantity of the adsorbent that contacts with alcoholic beverage also will influence the amount of the component of removing.The amount that is added to the adsorbent in the beer is measured (the gram number of the adsorbent of for example per 1,000,000 gram beer) with every a few millionths.The adsorbent consumption can be by 100ppm to about 1000ppm, and preferably about 400ppm about 800ppm extremely.
In the subtractive process of beer, sometimes with other additive absorbed component and implement other functions.Adsorbent of the present invention is that function of the present invention is assigned in other known in industry additives existence.For example, before filtration, in beer, add foam stabiliser, antioxidant, perlite and diatomite usually.For example, diatomite is used as filter aid, but does not wish to contribute in beer iron usually.
No matter the used particular adsorbent of the present invention, adsorbent (or several adsorbent) is separated in adsorbing afterwards by the alcoholic beverage of removing component with any known way.For example, filter can be used for by separating adsorbent in the alcoholic beverage of removing component.Separation can realize by one or more filtration steps.
Adsorbent of the present invention is the adsorbent that comprises silica component and polyphosphate chelator component.Be sure of shown in the accompanying drawing 1 in the embodiment, chemical bonded refractory between polyphosphate chelating agent and silica gel, and shown in the accompanying drawing 2 in the embodiment, its only physics remain in the hole of silica gel.Therefore, in precedent, silica gel and polyphosphate chelating agent can change sometimes each other, and thus, in final products, they are called as silica gel " component " and polyphosphate chelating agent " component ".Yet, in one embodiment of back, be sure of between two kinds of compositions without any chemical reaction.
Embodiment
Below listed embodiment all character of the present invention more clearly are described.These embodiment are exemplary, are not to be used to limit the present invention.
Embodiment 1
In an embodiment of the method for preparing product of the present invention, STPP is dissolved in the water, and allows with sodium metasilicate and at room temperature mixed 5 hours.With the sodium metasilicate is benchmark, and the silicate mixture that this STPP mixes contains the STPP of 0.1 weight %.The concentration of acid solution is 14.4% sulfuric acid, and temperature is about 72 °F.The standard SiO of this silicate solutions
2: Na
2The O weight ratio is 3.25, and solid content is 22%, and temperature is about 72 °F.Regulate silicate and sour concentration and ratio, make the hydrosol contain 10% SiO
2, and make have than in and the sodium that exists in the silicate solutions is required Duos 20% acid.The hydrosol can be at 122 gels in container.Gel time is several hours.At 122 aging these gels and with the acidifying water washing, give acidity then with sulfuric acid.The pH value that is used to remove the acidifying water of sodium sulphate is 3.3.This is the described sample 1 of table 1.
In order to contrast, use the method identical to make control sample 1 with sample 1, just do not add STPP.
Iron level is represented whole iron (Fe) in the gel.All iron and alcoholic beverage soluble iron (BSI) absorb (AA) measurement with atom.Whole iron contents of sample 1 are 83ppm, and BSI content is 2.4ppm, and whole iron contents of control sample 1 are 27ppm, and BSI content is 7ppm.
Embodiment 2
In another embodiment of the inventive method, except the concentration that increases STPP, the preparation method of silica gel is identical with embodiment 1.With the sodium metasilicate is benchmark, and the STPP among the embodiment 2 is 0.15 weight %.Also make control sample 2 and be used for comparison, use identical method in the sample 1, except in control experiment, not using STPP.
Embodiment 3
At the embodiment of second embodiment that is used for making adsorbent of the present invention, by with in the sulfuric acid and sodium metasilicate make silica gel.The concentration of acid solution is 41.8% H
2SO
4, temperature is about 80 °F.The standard SiO of silicate solutions
2: Na
2The O weight ratio is 3.2, and solid content is 31.4%, and temperature is 80 °F.Regulate silicate and sour concentration and ratio, make the hydrosol contain 18% SiO
2, and make have in and required many 20% the acid of sodium that exists in the silicate solutions.STPP is at first dissolved in the preparation of the aqueous acid that STPP mixes in water, the STPP concentration that with water is benchmark is 50ppm, is 3.4 by the pH value of adding sulfuric acid regulation solution then.Regulate the ratio of gel and washings, make with the sodium metasilicate to be benchmark, the total amount of used STPP equals 0.1 weight %.This is the sample 3 shown in the table 1.
By being that 3.4 the same gel of acid rinsing makes control sample 3 with the pH value.In this control experiment, do not use STPP.Whole iron contents of sample 3 are 5ppm, and BSI content is 0.2ppm, and whole iron contents of control sample 3 are 19ppm, and BSI content is 6.3ppm.
Embodiment 4
Another embodiment in second embodiment of the method that is used for making adsorbent uses same unwashed silica hydrogel.The preparation of the acid rinsing solution that STPP mixes at first by the pH value to 3.5 of regulator solution, is dissolved STPP then in sour water, the concentration that makes STPP is that benchmark is 200ppm with water.Regulate the ratio of gel and washings, make with the sodium metasilicate to be benchmark, the total amount of used STPP equals 0.5 weight %.Made under these conditions silica gel is the sample 4 in the table 1.
Control sample 4 is to make under 3.5 similarity conditions using same sour water pH value also, does not just add STPP.
Whole iron contents of sample 4 are 6.5ppm, and BSI content can not record with atomic adsorption (AA).Whole iron contents of control sample 4 are 20ppm, and BSI content is 5ppm.
All embodiment show that when using adsorbent of the present invention, BSI content lowers.Use the embodiment of embodiment shown in Figure 2 also to show the attenuating of whole iron contents.
At the BSI of this used adsorbent is according to American Society of BrewingChemist Methods, the program No.Q.2.01004 of Filter Aids-4 and Beer-18B, revision April 26,1994 measures, and is incorporated herein by reference at this.Usually, this program is included in except that hanging sample of sorbent certain hour, isolated by filtration then in the carbonic acid beer.Collect beer filtrate and use atomic absorption spectroscopy with standard increase method.The iron content of beer of being untreated then deducts the iron content of treated beer, and this difference multiply by a factor, and product is reported as the beer soluble iron of representing with ppm.
Though illustrate with reference to some particular and embodiment and describe that at this present invention can not be defined to shown in the embodiment.In addition, do not departing under the spirit of the present invention, with the scope of claim equivalence in can do various changes.
Claims (27)
1. method for preparing silica gel absorber with LA soluble iron content, this method may further comprise the steps:
The polyphosphate chelating agent is contacted with one of the reactant of described at least silica gel and the wash solution that contains described silica gel parent; And
Form silica gel absorber by described parent.
2. method as claimed in claim 1, wherein:
Described reactant comprises sodium metasilicate or potassium silicate; And
Described contact procedure is made up of to form mixture the solution that makes described polyphosphate chelating agent and described sodium metasilicate or potassium silicate contact and form described polyphosphate chelating agent and described sodium metasilicate or potassium silicate.
3. method as claimed in claim 2, it also comprises and adding in the sour extremely described mixture to form the hydrosol.
4. method as claimed in claim 2, wherein said polyphosphate chelating agent is a sodium phosphate trimer.
5. method as claimed in claim 1, wherein;
Described contact procedure is formed by described polyphosphate chelating agent is contacted with the described wash solution that contains described parent; And
Described parent comprises the hydrogel that forms by mixed acid and sodium metasilicate or potassium silicate.
6. method as claimed in claim 5, wherein said polyphosphate chelating agent is a sodium phosphate trimer.
7. method as claimed in claim 1, wherein said contact procedure comprise makes described polyphosphate chelating agent contact with described reactant, and contacts with the described wash solution that contains described parent.
8. method for preparing silica gel absorber with LA soluble iron content, this method may further comprise the steps:
The polyphosphate chelating agent is mixed with sodium metasilicate or potassium silicate to form mixture;
Add acid and to described mixture, have the silica hydrosol of polyphosphate component, and allow that described hydrosol sedimentation is a hydrogel with formation.
Wash described hydrogel with acidifying water; And
Grind described hydrogel to form the silica gel absorption body.
9. method as claimed in claim 8, wherein said acid are inorganic acid.
10. method as claimed in claim 8, wherein said polyphosphate chelating agent is a sodium phosphate trimer.
11. as the method for claim 10, wherein:
Described sodium metasilicate or potassium silicate have iron content;
Described sodium phosphate trimer is to reach sodium phosphate trimer: the mol ratio of iron is 0.5: 1-50: 1 amount joins in described sodium metasilicate or the potassium silicate;
Described acid joins in the described mixture with described sodium or the potassium of neutralizing fully with the amount of 5 moles of %-30 moles of amount % of being higher than the required acid of stoichiometry; And
The pH value of described acidifying water is 2.5-4.0.
12. as the method for claim 10, wherein:
Described sodium metasilicate or potassium silicate have iron content;
Described sodium phosphate trimer is to reach sodium phosphate trimer: the mol ratio of iron is 5: 1-10: 1 amount joins in described sodium metasilicate or the potassium silicate;
Described acid joins in the described mixture with described sodium or the potassium of neutralizing fully with the amount of 15 moles of %-25 moles of amount % of being higher than the required acid of stoichiometry; And
The pH value of described acidifying water is 3.2-3.4.
13. a method for preparing the silica gel absorber with LA soluble iron content, this method may further comprise the steps:
Sodium metasilicate or potassium silicate are mixed with the formation hydrosol with acid, and allow that described hydrosol sedimentation is a hydrogel;
The acidifying mixture of water and polyphosphate chelating agent washs described hydrogel; And
Grind described hydrogel to form silica gel absorber through washing.
14. as the method for claim 13, wherein said acid is inorganic acid.
15. as the method for claim 13, wherein said polyphosphate chelating agent is a sodium phosphate trimer.
16. as the method for claim 15, wherein:
Described sodium metasilicate or potassium silicate have iron content;
With the sodium metasilicate is benchmark, and described sodium phosphate trimer is that the amount of the sodium phosphate trimer of 0.01-1 weight % joins in the described acidifying mixture to reach concentration;
Described acid joins in the described mixture with described sodium or the potassium of neutralizing fully with the amount of 5 moles of %-30 moles of amount % of being higher than the required acid of stoichiometry; And
The pH value of described acidifying water is 2.5-4.0.
17. as the method for claim 15, wherein:
Described sodium metasilicate or potassium silicate have iron content;
With the sodium metasilicate is benchmark, and described sodium phosphate trimer is that the amount of the sodium phosphate trimer of 0.05-0.5 weight % joins in the described acidic mixture to reach concentration;
Described acid joins in the described mixture with described sodium or the potassium of neutralizing fully with the amount of 15 moles of %-25 moles of amount % of being higher than the required acid of stoichiometry; And
The pH value of described acidifying water is 3.3-3.5.
18. one kind is used for removing component to lower the composition of chill haze by alcoholic beverage, described composition comprises the adsorbent that contains silica component and polyphosphate chelator component.
19. as the composition of claim 18, wherein:
Described silica component is a silica gel; And
Described polyphosphate chelator component is a sodium phosphate trimer.
20. one kind by removing component to lower the method for chill haze in the alcoholic beverage, said method comprising the steps of:
Alcoholic beverage is contacted with the adsorbent that comprises silica component and polyphosphate chelator component, be adsorbed to the described component of small part to described adsorbent, obtain the alcoholic beverage of low component thus; And
By separating described adsorbent in the described low component alcoholic beverage.
21. as the method for claim 20, wherein:
Described silica component is a silica gel; And
Described polyphosphate chelator component is a sodium phosphate trimer.
22. as the method for claim 21, wherein said adsorbent serves as that the amount of the about 1000ppm of about 100ppm-joins in the described alcoholic beverage to reach concentration.
23. as the method for claim 21, wherein said adsorbent serves as that the amount of the about 800ppm of about 400ppm-joins in the described alcoholic beverage to reach concentration.
24. as the method for claim 21, wherein said separating step comprises by filtering described adsorbent in the alcoholic beverage of described low component.
25. pass through the silica gel absorber that the method for claim 1 forms.
26. pass through the silica gel absorber that the method for claim 8 forms.
27. pass through the silica gel absorber that the method for claim 13 forms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/760,353 US6555151B2 (en) | 2001-01-12 | 2001-01-12 | Process for making and using a low beverage soluble iron content adsorbent and composition made thereby |
| US09/760,353 | 2001-01-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1503693A true CN1503693A (en) | 2004-06-09 |
| CN1284620C CN1284620C (en) | 2006-11-15 |
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|---|---|---|---|
| CNB02803659XA Expired - Fee Related CN1284620C (en) | 2001-01-12 | 2002-01-14 | Process for making and using a low beverage soluble iron content adsorbent and composition made thereby |
Country Status (11)
| Country | Link |
|---|---|
| US (2) | US6555151B2 (en) |
| EP (1) | EP1385620A2 (en) |
| JP (2) | JP2004530533A (en) |
| KR (1) | KR20030077574A (en) |
| CN (1) | CN1284620C (en) |
| AU (1) | AU2002234246A1 (en) |
| BR (1) | BR0206382A (en) |
| CA (1) | CA2433658A1 (en) |
| MX (1) | MXPA03006304A (en) |
| WO (1) | WO2002055190A2 (en) |
| ZA (1) | ZA200305278B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788989A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Steam cracking method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2857599B1 (en) * | 2003-07-16 | 2006-02-24 | Realdyme | BIOLOGICAL METHOD FOR DETOXING A FOOD LIQUID MEDIUM AND DETOXIC FOOD LIQUID MEDIA OBTAINED ACCORDING TO THIS PROCESS |
| US7229655B2 (en) * | 2003-12-30 | 2007-06-12 | Pq Corporation | Composition of, and process for using, silica xerogel for beer stabilization |
| US7767621B2 (en) * | 2006-08-25 | 2010-08-03 | World Minerals, Inc. | Processes for reducing beer soluble iron in diatomaceous earth products, diatomaceous earth products and compositions thereof, and methods of use |
| CN105712357A (en) * | 2008-09-26 | 2016-06-29 | 英默里斯筛选矿物公司 | Diatomaceous earth products containing reduced soluble metal levels, preparation method thereof and methods of using the same |
| US20110180470A1 (en) * | 2010-01-27 | 2011-07-28 | James Jeffrey Harris | Aqueous iron removal process and apparatus |
| US9005687B2 (en) * | 2010-03-15 | 2015-04-14 | Millercoors Llc | Methods for reducing soluble metal ions in diatomaceous earth filter aids |
| RU2015114330A (en) | 2012-09-17 | 2016-11-10 | У.Р. Грейс Энд Ко.-Конн. | CHROMATOGRAPHIC MEDIA AND DEVICES |
| ES2929099T3 (en) | 2014-05-02 | 2022-11-24 | Grace W R & Co | Functionalized support material and methods of manufacturing and use of functionalized support material |
| JP2018517559A (en) | 2015-06-05 | 2018-07-05 | ダブリュー・アール・グレース・アンド・カンパニー−コーンＷ Ｒ Ｇｒａｃｅ ＆ Ｃｏ−Ｃｏｎｎ | Adsorbing bioprocess clarifier and method for producing and using the same |
| IT201800004721A1 (en) | 2018-04-19 | 2019-10-19 | Device for the stabilization of wine and other vegetable drinks and related stabilization process. | |
| CN111747419B (en) * | 2020-07-08 | 2023-08-22 | 青岛美高集团有限公司 | Method for reducing heavy metal content in silica gel |
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| GB1215928A (en) | 1967-04-28 | 1970-12-16 | Unilever Ltd | A process for reducing haze in beer |
| CH510115A (en) * | 1968-11-22 | 1971-07-15 | Brauerei Ind Ag F | Process for making an adsorbent |
| US3800031A (en) * | 1972-04-06 | 1974-03-26 | Grace W R & Co | Process for preparing silica hydrogel |
| US3846337A (en) * | 1972-07-20 | 1974-11-05 | Union Oil Co | Phosphate-silica-aluminosilicate compositions of improved crushing strength and methods of preparing the same |
| US4134857A (en) | 1977-02-07 | 1979-01-16 | Johns-Manville Corporation | Use of tannic or gallic acid to produce low beverage soluble iron content filter aid |
| FR2471949A1 (en) | 1979-12-20 | 1981-06-26 | Rhone Poulenc Ind | Fine silica prepn. - by reaction of alkali metal and acid using sequestering agent to complex with impurity metallic ions(BR 7.7.81) |
| US4508742A (en) | 1983-05-06 | 1985-04-02 | Pq Corporation | Treating beer to prevent chill haze and metal contamination |
| US4847235A (en) * | 1986-02-03 | 1989-07-11 | Scm Glidco Organics Corp. | Silica product |
| US4758440A (en) * | 1986-02-03 | 1988-07-19 | Heem Peter V D | Process for chillproofing a malt beverage and silica product for chillproofing |
| US5215733A (en) * | 1986-04-25 | 1993-06-01 | Unilever Patent Holdings B.V. | Manufacture of silica gels using shear to reduce the particle size prior to washing with a hydrocyclone |
| GB8707526D0 (en) | 1987-03-30 | 1987-05-07 | Unilever Plc | Amorphous silicas |
| US4847532A (en) * | 1988-05-27 | 1989-07-11 | Tektronix, Inc. | Tensed shadow mask assembly for cathode-ray tube |
| JPH038710A (en) * | 1989-06-05 | 1991-01-16 | Jgc Corp | Production of fine silica gel powder having high filterability |
| US5641532A (en) * | 1995-12-15 | 1997-06-24 | The Procter & Gamble Company | Beverages having stable flavor/cloud emulsions in the presence of polyphosphate-containing preservative systems by including gellan gum |
| AU4696500A (en) | 1999-05-03 | 2000-11-17 | Pq Holding, Inc. | Process and composition for reducing chill haze in beverages |
| RU2160777C1 (en) * | 2000-02-16 | 2000-12-20 | Открытое акционерное общество "Воскресенские минеральные удобрения" | Bear clarification method |
-
2001
- 2001-01-12 US US09/760,353 patent/US6555151B2/en not_active Expired - Lifetime
-
2002
- 2002-01-14 CN CNB02803659XA patent/CN1284620C/en not_active Expired - Fee Related
- 2002-01-14 MX MXPA03006304A patent/MXPA03006304A/en active IP Right Grant
- 2002-01-14 WO PCT/US2002/001005 patent/WO2002055190A2/en active Application Filing
- 2002-01-14 EP EP02701048A patent/EP1385620A2/en not_active Withdrawn
- 2002-01-14 BR BR0206382-4A patent/BR0206382A/en not_active IP Right Cessation
- 2002-01-14 KR KR10-2003-7009304A patent/KR20030077574A/en not_active Application Discontinuation
- 2002-01-14 JP JP2002555914A patent/JP2004530533A/en active Pending
- 2002-01-14 AU AU2002234246A patent/AU2002234246A1/en not_active Abandoned
- 2002-01-14 CA CA002433658A patent/CA2433658A1/en not_active Abandoned
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2003
- 2003-03-17 US US10/390,361 patent/US20030170361A1/en not_active Abandoned
- 2003-07-08 ZA ZA200305278A patent/ZA200305278B/en unknown
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2007
- 2007-09-18 JP JP2007241602A patent/JP2008080332A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788989A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Steam cracking method |
| CN103788989B (en) * | 2012-10-29 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of steam cracking method |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2433658A1 (en) | 2002-07-18 |
| WO2002055190A3 (en) | 2003-11-13 |
| CN1284620C (en) | 2006-11-15 |
| JP2004530533A (en) | 2004-10-07 |
| AU2002234246A1 (en) | 2002-07-24 |
| US20030170361A1 (en) | 2003-09-11 |
| US6555151B2 (en) | 2003-04-29 |
| US20020094364A1 (en) | 2002-07-18 |
| EP1385620A2 (en) | 2004-02-04 |
| MXPA03006304A (en) | 2003-09-16 |
| ZA200305278B (en) | 2004-10-20 |
| JP2008080332A (en) | 2008-04-10 |
| KR20030077574A (en) | 2003-10-01 |
| BR0206382A (en) | 2004-02-03 |
| WO2002055190A2 (en) | 2002-07-18 |
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